Builders for detergent and cleansing agents

ABSTRACT

Water-soluble salts of acid carboxylic acid esters of bivalent aliphatic or olefinically unsaturated carboxylic acids or hydroxycarboxylic acids and at least trihydric aliphatic alcohols are used as builders for detergent and cleansing agents. Each hydroxylic group of the alcohol or optionally of the carboxylic acid has a carboxylic acid-molecule attached thereto.

252-99. AU 165 EX United States Patent [1 1 Kandler et al.

BUILDERS FOR DETERGENT AND CLEANSING AGENTS Inventors: Joachim Kandler,

Erftstadt-Lechenich; Karl Merkenich, Efferen; Klaus Henning, l-Iurth;Wilhelm Vogt, Efferen; Eberhard Auer, Erftstadt-Liblar; Hermann Glaser,Erftstadt-Lechenich, all of Germany Assignee: l'loechstAktiengesellschaft, Cologne,

Germany Filed: Sept. 21, 1972 Appl. No.: 291,043

Foreign Application Priority Data Sept. 24, 1971 Germany 2147780 US. Cl.252/96; 252/89; 252/95; 252/99; 252/135; 252/DIG. l; 252/D1G. 2;252/D1G. 6; 260/485 G Int. Cl Clld 9/42 1 July 1, 1975 [58] Field ofSearch..... 252/D1G. l, DIG. 2, DIG. 6,

Primary Examiner-Leland A. Sebastian Attorney, Agent, or Firm-Connolly &Hutz 57 ABSTRACT Water-soluble salts of acid carboxylic acid esters ofbivalent aliphatic or oletinically unsaturated carboxylic acids orhydroxycarboxylic acids and at least trihydric aliphatic alcohols areused as builders for detergent and cleansing agents. Each hydroxylicgroup of the alcohol or optionally of the carboxylic acid has acarboxylic acid-molecule attached thereto.

2 Claims, 2 Drawing Figures BUILDERS FOR DETERGENT AND CLEANSING AGENTSThe present invention provides builders for detergents and cleansingagents, the builders comprising water-soluble salts of acid carboxylicacid esters and the esters being the product obtained by the reaction ofbivalent carboxylic acids with polyhydric alcohols.

it has already been reported that the cleansing power of soaps andsynthetic detergents in detergent and cleansing agents can be improvedby means of certain addends. These cleansing intensifiers are termedbuilders. Detergent and cleansing agents having such builders thereinare more effective. yet less costly than corresponding formulationswhich are free from builders.

The mechanism and the details of the "builder effect have not yet beenfully described. Vital to the function of the builder is a plurality ofprocesses comprising. for example: the stabilization of pigment dirtsuspensions; the emulsification of dirt particles; the effect on thesurface and interfacial properties of aqueous tenside solutions; thesolubilization of waterinsoluble ingredients of the cleansing bath; thepeptization of agglomerated dirt; the neutralization of acid substances;and the inactivation of mineral matter in the cleansing bath.

To determine the quality and qualification of individual materials foruse as a builder. it is good practice to test their behaviour andefficiency in washing or cleansing operations. to ensure the qualitativeand quantitative determination of all factors that make theircontribution to the builder effect.

Classical builders comprise water-soluble inorganic alkali metal salts.such as alkali metal carbonates. bo-

rates. phosphates. polyphosphates. bicarbonates. and silicates.

While a plurality of materials have been suggested for use as builders.the fact remains that linear condensed phosphates or polyphosphates,more particularly pentasodium triphosphate or sodium tripolyphosphate.are almost exclusively used as the builders in customary detergent andcleansing agents having up to substantially 50 weight percent buildertherein.

The considerably increased consumption of phos phate-containingdetergent and cleansing agents both for domestic and industrial purposeshas also effected an increase in the phosphate content of naturalwaters. In studies of the eutrophication of waters. which has been foundto occur at increasing rates. the nitrates and phosphates have recentlybeen held to have properties that are able under certain conditions topromote the growth of certain alga species, and thereby to make theircontribution to the eutrophication of water. Even though it isimpossible for the time being definitely to clarify this problem. namelythe contribution of detergents and cleansing agents to theeutrophication of water, it is highly desirable to have potentialsubstitutes free from nitrogen and phosphorus for the builders. namelypolyphosphates. that find widespread use in current detergentformulations.

Compounds which are free from nitrogen and phosphorus have already beensuggested for use as builders in detergents. Starch derivatives. such asdicarboxyl and carboxymethyl starch. polycarboxylic acids. such aspolymaleic acid and the copolymers thereof. oxydiacetic acid.oxydisuccinic acid. esters containing sulfonate groups of polyethyleneglycol and adipic acid or maleic acid. and esters of ethylene glycol andtrior tetf racarboxylic acids. have more particularly been usedheretofore. The use of these substances as builders has 5 been found toentail disadvantages which reside in the fact that they areinsufficiently biodegradable or have an unsatisfactory power fordispersing hydrophilic dirt.

Still further. there partially is a lack of processes per- E mittingthese substances to be made under commercially attractive conditions. Inaddition to the tenside constituent. which merely enables hydrophobicdirt. such as carbon black and fat particles. to be dispersed and/orpeptized. it is necessary for a detergent to contain a furtheringredient removing hydrophilic dirt. namely a builder. in the ab- Wehave now unexpectedly discovered that watersoluble salts of acidcarboxylic acid esters produced from bivalent aliphatic or olefinicallyunsaturated carboxylic acids or hydroxycarboxylic acids and at least 4trihydric alcohols. each hydroxylic group of the alcohol and optionallyof the carboxylic acid having a carboxylic acid-molecule attachedthereto. are very suitable for use as builders in detergents andcleansing agents. as they have an efficiency excelling that ofconventional builders free from nitrogen and phosphorus.-

The cation of the water-soluble salts of acid carboxylic acid esterspreferably is an alkali or ammonium ion. whereas the ester-type anion isbased on a bivalent carboxylic acid. which has between 2 and 6 carbonatoms and is esterified with a polyhydric alcohol containing betweenthree and six hydroxylic groups.

in accordance with the present in ention. the acid component of thecarboxylic acid esters should be selected. for example. from the groupconsisting of oxalic acid. malonic acid. maleic acid. succinic acid.oxydiacetic acid, tartaric acid. malic acid or itaconic acid. and thealcoholic component should be selected from the group consisting ofglycerol. erythritol. pentaerythritol. mannitol. sorbitol or a sugaralcohol having between 4 and 6 carbon atoms.

To produce detergent and cleansing agents. it is possible to introducethe ester salt builders of the present invention into conventionaldetergent and cleansing agents. which are based on ion-active and/ornon-ionic tensides and which may optionally contain further ad-' dends.In accordance with the present invention. the builder may generally beused in a proportion substantially between 10 and 80 weight percent.preferably between l5 and 60 weight percent, based on the dry sub- 5phates or their substitutes specified hereinabove. Detergent andcleansing agents prepared in accordance with the present invention givea pH-value between 8 Q and I2 in the aqueous medium of the wash bath.

The addends. which may be present together with the ion-active and/ornon-ionic tensides in the detergents comprise substances. such as alkalimetal or ammonium salts of sulfuric acid. silicic acid. diand trisilicicacids. carbonic acid. boric acid. iminodiacetic acid. nitrilotriaceticacid. ethylene diamine tetracetic acid. al-

a 3 kylene phosphonic acids. hydroxyalkylene phosphonic acids and/oraminoalkylene phosphonic acids. or stabilizers and activators forperborates. as well as optical brighteners. carboxymethyl cellulose.magnesium silicate. disinfectants and/or enzymes. for example.

The carboxylic acid esters underlying the builder salts of the presentinvention are produced by conventional esterification methods. forexample. by reacting the acid with the alcohols and simultaneouslyremoving the reaction water by means of an expelling agent. The acid andalcohol should generally be used in a molar j ratio such that onemolecule of the bivalent carboxylic acid be available. per alcoholichydroxylic group. In those cases in which the carboxylic acid itselfcontains one or more hydroxylic groups. it is also possible to esterifythese groups. In this case. the quantitative ratio between acid andalcohol is accordingly greater than the number of the hydroxylic groupsin the polyhydric alcohol. During the esterification. it is necessaryand critical to remove from the esterification mixture one mol ofreaction water. per mol of carboxylic acid used. The resulting acidcarboxylic acid esters are transformed into water-soluble salts by theaddition of stoichiometric proportions of alkali.

The builders of the present invention offer technically very beneficialeffects as they considerably delay the precipitation of calcium ions inthe wash bath and additionally do form stable dispersions withhydrophilic pigment particles. A further beneficial effect resides inthe fact that they are readily biodegradable and thereby prevented fromconcentrating in natural waters.

The properties of the builders of the present invention can beevaluated. for example. by identifying their power of dispersing iron(lll) oxide. their power of binding calcium ions and their washingefficiency on washing an artificially soiled fabric. Suitable tests weremade with the builders of the present invention and the results obtainedwere compared wtih the properties of conventional builders. The testswere more particularly carried out in the manner described in thefollowing Examples.

EXAMPLE 1 The following novel builders: A: Sodium salt ofglycerol-tri-oxydiacetic acid B: Sodium salt ofsorbitol-hexa-oxydiacetic acid C: Sodium salt of glycerol-tri-malic acidwere tested as to their dispersing effect in an aqueous suspension of 4weight percent of dry. pulverized iron (lll) oxide with a particle sizeof less than 0.058 mm, and the effect produced was compared with thatproduced by conventional builders. namely: D: Oxydiacetic acid E: Malicacid F: Glycerol G: Diacetin H: Sodium salt of citric acidethyleneglycol ester. Each ofthe builder was used in the suspension in aconcentration of 0.16 weight percent. based on the aqueous solution. Thesettling time of the iron oxide part cles in cc mixing cylinders. andthe volume of sedlmentation after 24 hours were determined in each cast.as an index of the dispersing effect. The suspension had a pH-value of10. The results obtained are summarized in Table 1 below.

Table l Builder Sedimentation volume Settling time in milliliters inhours A 1.40 20 B L45 l8 C 1.40 17 D unstable unstable E unstableunstable F unstable unstable G unstable unstable H 1.5 16

As can be seen from Table l. the novel builders had a dispersing effecton hydrophilic dirt particles which was better than that of conventionalbuilders. This results from both the smaller sedimentation volume andlower settling rate.

EXAMPLE 2 The builders specified in Example 1 were tested as to theirpower of binding calcium ions. The power of binding calcium ions in anaqueous solution is defined by the number identifying the grams ofcalcium ions kept in solution under certain conditions. by lOO grams ofbuilder. This number is determined by titration with sodium carbonate.More particularly. a 1 percent test solution with a pH-value of 10 wastitrated with a 0.1N calcium chloride solution until turbidity commencedto occur. The following numerical values indicating the power of bindingcalcium ions were determined for the individual builders (Table 2).

As can be seen from Table 2. the novel builders were found to combinethe good dispersibility of Table l with a good power for binding Ca-iOnS. As compared therewith, conventional builders could not be foundto have these two properties at the same time to the same extent.

EXAMPLE 3 Wash tests were made to determine the cleansing powerquotients of wash liquors which for a constant concentration of surfaceactive substance contained varying proportions of the builders of thepresent invention specified in Example I. and the test results obtainedwere graphically plotted in FIG. 1 of the accompanying graphs. curvesA-C. Analogous wash tests with the use ofthe conventional builders,specified in Example l. were made for the purpose of comparison. and thecleansing power quotients were also graphically plotted in FIG. 1.curves D. E. G and H.

The wash tests were made on standard cotton fabrics soiled with Krefeld"dirt in a Launder-O-meter" at a wash bath temperature of C. Standardfabrics soiled with Krefeld dirt have been defined by Kurt Lindner inthe book entitled: Tenside. Textilhilfsmit- 30 minutes and the bathratio. expressed by the ratio of material to be washed in kg to washliquor in liter was 1:50. and the wash operation was carried out in thepresence of steel balls. The wash liquor contained as surface-activesubstances 0.45 g/liter of dodecylbenzene sulfonate.

0.15 g/liter of tallow fatty oil and O.l5 g/liter of hardened tallowsoap.

The builders were used in the wash liquor in a concentration between 0.2and 2 grams/liter of wash liquor.

After the prescribed wash time. the standard cotton fabric was rinsed,once hot and once cold. and its degree of whiteness was then determinedusing an Elrepho remission photometer. (a product of Zeiss) and a filterR 53. Based on the test result obtained, the cleansing power quotientwas calculated according to the following formula:

the builder employed in accordance with the present invention than bythe conventional builders D. E. G and H.

EXAMPLE 4 The procedure was the same as that described in Example 3.save that the following additional ingredients were introduced into thewash liquor;

0.15 g of magnesium silicate/liter of wash liquor.

0.15 g of sodium silicate/liter of wash liquor,

1.25 g of sodium perborate tetrahydrate/liter of wash liquor.

0.45 g of sodium sulfate/liter of wash liquor. and

0.05 g of Tylose/liter of wash liquor.

The wash results obtained were graphically plotted in FIG. 2, curvesA-C. As can be seen, the builders used in accordance with the presentinvention were found to distinguish favorably over the conventionalbuilders (curves D. E. G and H).

PREPARATION OF THE BUILDERS USED IN ACCORDANCE WITH THIS INVENTION.

The builders used in Examples 1 to 4 were not specifically purifiedduring preparation. In other words. the reaction products (crudeproducts) directly obtained following termination of the esterificationof the polyvalent carboxylic acid with the polyhydric alcohol andfollowing neutralization of the resulting esterification mixtures, wereused. This is further illustrated in the following Examples.

EXAMPLE 5 A mixture of 92 parts by weight of glycerol and 402 parts byweight of oxydiacetic acid was subjected to azeotropic distillation with250 parts by weight of toluene. which was continuously recycled. so asto remove 54 parts by weight of reaction water, which did form duringthe esterification. The mixture was cooled and the toluene was separatedfrom the ester layer. To produce the sodium salt, the acid crude esterwas neutralized with 300 parts by weight of 40 percent sodium hydroxidesolution and the resulting neutralization mixture was dried undervacuum. The product so obtained was used as builder A in Examples 1 to4.

EXAMPLE 6 A mixture of 182 parts by weight of sorbitol and 804 parts byweight of oxydiacetic acid was subjected to azeotropic distillation with250 parts by weight of tolu ene, which was continuously recycled. so asto remove 180 parts by weight of reaction water. The ester was cooledand the toluene was separated from the ester I layer. To produce thesodium salt. the crude ester was neutralized with 600 parts by weight of40 percent sodium solution and the resulting neutralization mixture wasdried under vacuum. The product so obtained was used as builder B inExamples 1 to 4.

We claim: I. A detergent composition containing dodecylben zenesulfonate. tallow oil, hardened tallow soap, magnesium silicate, sodiumsilicate, sodium perborate tetrahydrate. sodium sulfate. and a builder.the builder being a substance selected from the group consisting of thesodium salt of glycerol-trioxydiacetic acid, the sodium salt ofsorbitol-hexaoxydiacetic acid and the sodium salt of glycerol trimalicacid, the builder being present in a proportion between 10 and weightperally contains an alkali metal polyphosphate builder.

1. A DETERGENT COMPOSITION CONTAINING DODECYLBENZENE SULFONATE, TALLOWOIL, HARDENED TALLOW SOAP, MAGNESIUM SILICATE, SODIUM PERBORATETETRAHYDRATE, SODIUM SULFATE, AND A BUILDER, THE BUILDER A SUBSTANCESELECTED FROM THE GROUP CONSISITING OF THE SODIUM SALT OFGLYCEROL-TRIOXYDIACETIC ACID, THE SODIUM SALT OFSORBITOL-HEXAOXYDIACETIC ACID AND THE SODIUM SALT OF GLYCEROL TRIMALICACID, THE BUILDER BEING PRESENT IN A PROPORTION BETWEEN 10 AND 80 WEIGHTPERCENT BASED ON THE TOTAL DRY INGREDIENTS OF THE COMPOSITION.
 2. Thedetergent composition according to claim 1 wherein the builder ispresent in an amount between 15 and 60 weight percent and thecomposition additionally contains an alkali metal polyphosphate builder.